Slovent for pyroxylin, &amp;c., and process for making the same.



' UNITED" sTAt s rrENT OFFICE.

HENRY V. WALKER, OF BROO KLYN, NEW YORK, ASSIGNOR TO THE MAAS & WALD- STEIN COMPANY, OF NEWARK, NEW JERSEY, A GQBPORATION OF NEW JERSEY.

- R Drawing.

' SLOVEN'I FOR-PYROX YLIN, &c., AND PROCESS FOR MAKING THE SAME.

Specification of Letters Patent. Patented Oct. 18, 1910. Application filed January 21, 1909. -Serial No. 473,499.

To all whom it may concern:

Be it known that I, HENRY V. \VALKER, a citizen of the United States, and resident of Brooklyn, in the county of Kings and State of New York, have invented certain new and useful' Improvements in Solvents for Pyroxylin, &c., and Processes for Maklated to my taneous herewith, for United States Letters- Patent Serial: No. 473,498, and is also re-' rocess for making chlorhydrins, the sub ectof my application, simultaneous herewith, for United States Letters Patent Serial No. 473,497. As-examples of "the'newsolvents withinmy present invention, I have specifically 'named gas-naphtha olefin oxids, and will now proceed to describe their method of preparation and the characteristics of the solventsthemselves.

My preferred starting material is s'ocalled gas-naphtha, a by-product of the ordinary commercial treatment of petroleum.

Thus, in the process of refining crude petro leum, the 011 is subjected to distillation,

the lighter products, such as naphtha and benzin, comlng over first. These. are followed by the burning oil fraction. At a certain stage of thisperiod of the distillation, it is found that the product coming over is of'much lower boiling point, gravity and flashing point than that preceding it.

This fpeculiarity is attributed to a cracking up o the higher hydrocarbons under the influence of the high temperature prevailing in the distillation. It is usual to run the distillation until the product has again risen in gravity, etc., to that of the initial burning oil fraction. This, secondary product which is collected separately is then redistilled,

yielding a distillate called gas-naphtha and a residue which is added to theburning oil fraction. refineries as gas-naphtha has been so called:

from the use to which it has heretofore been.

This material known' in the OH,'CH,--CH,CH,CH=CH,.

As part of the process, I convert the olefins of this ture of olefins and parafiins as is contained in this gas-naphthawould react with hyas naphtha into chlorhydrins. It might e thought thatsuch a mixpochlorous acid produced in any of the I usual ways to form chlorhydrins (although so far as known to me no chlorhydrin or oxid ofa primary olefin having-five or more carbons has been so produced) but it was found not to be so. There are two described methods .of preparing hypochlorous acid.

The first of these depends essentially upon the reaction of chlorm with'mercuric oxid. This method is too expensive to be thought of on account of the great cost of the mercuric oxidi employed. The second of these comprises the treatment of hypochlorites of sodium, or calcium,-With a dilute acid. In each case free chlorin was present, the yield of hypochlorous acid was small and its solution was dilute. Both of these methods, therefore, were unavailable. I was, therefore, obliged to find another method of producing the hypochlorous acid. I discovered that if there was added to a solution of a suitable hypochlorite, for instance, hypochlorite of soda, a suflicient quantity of a suitable bicarbonate, for instance, bicarbonate of soda, to convert both the free alkali and the sodium in combination in the hypochlorite, into sodium carbonate, then a solution was'obtained which contained hy-- chlorous acid to make the aforesaid chlorhydrins from the gas-naphtha olefins as fol- -lows: Thus, the gas-naphtha, comprising a mixture of olefins and paraifins as stated or other suitable material containing the olefins, is first placed in a vessel provided with means for agitating and cooling its contents.

In another suitable vessel is placed a solution in water of a suitable hypochlorite, for

: be all three mixed together and-allowed to react in the same vessel. A solution of the hypochlorite containing from 15 to- 25 per cent. of NaOCl is of convenient strength.

' To this is added a sufiicient quantity of a produced. The mixture of hypochlorite and bicarbonate of soda in which the hypochlorous acid formed is then added to the vessel containing the gas naphtha, or other material, and the contents are agitated and cooled. The reaction will take place at ordinary temperatures without cooling, but the best results are obtained by preventing the rise of temperature due to the react-ion and maintaining the temperature at or below 15 centigrade. This reaction should continue for about four hours. At the end of that time the oily portion of the liquid containing the chlorhydrins is allowed to separate from the aqueous portion of the liquid, the latter being-drawn off and rejected. The oilyportion is then washed with a smallamount of water to remove any hypochlorite which might remain and it is dehydrated. If it is desired to accomplish such dehydration quickly, calcium chlorid may be employed. If time is not essential, the water may be allowed to separate out by gravity. The discovery upon which this part of the process depends is that the chlorhydrins remain in the oily part of the liquid andnot in its aqueous part. The paraflins, ;or residual hydrocarbons, which are mixed with the chlorhydrins are then removed. This is accomplished by distillation at a suitable temperature below the boiling point of the chlorhydrins, which is about 170 centigrade. Such a temperature is about 140 centigrade. Of course, the temperature during this step of the process must be lower than that at distillate is a mixture of olefin oxids;

which the chlorhydrins will be carried over.

.After such distillation, the residual liquid consists of the chlorhydrins sought to be obtained. I r

The reactions apparently involved may be illustrated in connection with the C olefin o NaOCl NaHCO, Na CO H001 2 O,H,, H001 0,11 011.01

(Chlorhydrin of the Cuolefiu.)

In carrying out the above part of the process, it is advisable first to ascertain the percentage of olcfins in the material employed by determining the amount of bromin absorbed, using the well known methods for this purpose. From this, the quantity of hypoehlorous acid necessary to be used is shown by the above equation No. 2, a slight excess of such acid bein used to insure as complete a conversion ot the olefins as possible. The next step in the process is to treat the residual chlorhydrins produced as above with a suitable caustic alkali. For thispurpose, I use the caustic alkalies, slaked lime, caustic potash or soda, preferring lime. In'practice, to: 1,000 grams of the chlorhydrins, 1 add amixture of about 350 grams of lime mlxed with about 1 liter of water. This chlorhydrin-lime mixture is heated to boiling in a suitable vessel with a return condenser for about one hour; it is then distilled with steam until no more oil passes over. This oil is-separated from the water and agitated while cold with a 50% solution of caustic soda for the purpose of removing a small portion of impurities which may be present. It is then separated and is dehydrated with-carbonate potash or calcium chlorid and distilled when it passes over as a water-white fluid. The described If desired, it may be separated by fractional distillation into separate parts but this is a v mere matter of expediency depending upon the partlcular use in view. These olefin oxids elt-her separately or as amixture' constitute a novel solvent for pyroxylin and other substances.

The gas naphtha, which is my preferred material for the production of the chlorhydrins, is a mixture of olefins and paraffins ranging from C 11,}, and 0 H to 0 H, and C H -Its boiling point. ranges from 30 C. to 125 C. By conversion into chlordydrins and decomposition with caustic alkali the olefins therein are converted into olefin oxids, from C HmO to C- H O. The olefin oxids of five or more carbon atoms,

heretofore produced have been of secondary or tertiary structure, whereas the olefins contarne 111 the gas naphtha are 10f normal or primary structure. The oxlds derlved there- 'from are therefore new bodies. These difj ferences in structure may be illustrated as follows, li reprcseutlug any alkyl radical:

i R (I! C H Primary, rharaeterizml hy the group 0 H l C=Hg Segondary, characterized by the group H 1-1 1 Tertiary, characterized by the preseuce of a nonhydrogenized carbon- The facts upon which itis claimed that the new olefin oxids made from gas-naphtha have the primary structure are as follows: 1. The paraflins of American petroleum are of primary structure;

2. The olefins produced by the action of heat on the paraflins are also of primary structure,

R-c=d-H (Armstron and Miller, Chem. Soc. 1886 I, 79-93.

Ber. (Re 19.244.)

3. I The olefin oxidsprepared by me do not combine with water. This is a characteristic property of primary olefin oxids as distinuished from the secondary or tertiary oxids, which do.combine with water to form glycols. I

'I am aware that Wurtz (A. ch. (4) A, 184) has described the preparation of a hexylenoxid, an olefin oxid at one time thought to possess the primary structure, and which was prepared from the hexylen derived from mannite, but subsequent investigations have shown .its' structure to be secondary. (Henry Oompt. Rand. 97,260.) The olefin oxids produced by me, therefore,

. are the first of the primary structure which have been made.

In some instances instead of separating the chlorhydrins from the paraflins as described, I may proceed as follows: .After reacting on the gas naphtha with the hypochlorous acid mixture and separating the oily from the aqueous portion, I may distil the entire oily layer directly with caustic.

alkali, without separating the parafiins. The oily portion of the resulting distillate, after separation and dehydration in. the usual manner, constitutes a novel solvent for various varnish gums, and when the percenta e of olefins in the primary material is ciently high, for pyroxylin.

The mixture of olefin oxlds produced as above described, and which constitutes a novelsolvent for pyroxylin possesses several important advantages. By its use pyroxylin may be obtained in strong transparent films, properties heretofore commercially obtainable only by the use of amyl acetate as a solvent. My novel solvent is produced from petroleum, a domestic product available in unlimited quantities, as contrasted with amyl acetate, roduced from fusel oil, mainly an importe roduct, of which the supply is necessarily limited. By the use of my novel solvent, pyroxylin may be em-fl ployed for many indicated purposes for which it hitherto could not be used, because of the high cost of amyl acetate. My novel solvent may also be employed not only as a solvent for pyroxylin, but for other substances such as rubber, asphalt, sundry varnish gums such as copal, kauri and the like, andoils such as boiled linseed-oil. The new solvent may also be diluted with a number ofother liquids such as benzin and similar. petroleum products which while not themselves solvents for the materials dissolved to a considerable extent with said solvent without annulling its solvent properties, For instance, if the new solvent is employed for dissolving pyroxylin it may be diluted with benzin even up to 30% in which dilution it will still dissolve pyroxylin although benzin itself does not dissolve this substance.

The olefin oxidsderived from gas naphtha have a slight ethereal odor, are insoluble in water, and range in specific gravity from about 0.830 toabout 0.855 and in .boiling points from-about 70 to about 145 by the new solvent, nevertheless are miscible reaction'product, and dlstilling the oily portion with a caustic alkali.

2. The process of preparing a novel: solvent which consists in mixing a bi-carbonate of a fixed alkali and a solution containing a hypochlorite of a fixed alkali, causing the mixture to react with gas naphtha, separating the oily from the aqueous portion of the reaction product,and distilling the oily portion with slaked lime.

3. As anew product of manufacture, an oxid of a primary olefin having 'approxi mately from five to eight carbon atoms, both inclusive.

4.. As a new product of'manufacture, an

oxid of a primary olefin obtained from proximately naphtha, having approximately from five to eight carbon atoms, both inclusive.

5. As a new product of manufacture, a mixture of a fprimary olefin oxid having aprom five to eight carbon atoms,

both inclusive, and a diluent, such as benzin, which mixture is capable of dissolving pyroxylin.

6. As a new product of manufacture, a mixture of an oxid of a primary olefin obtained from gas naphtha, and having approximately from five to eight carbon atoms, both inclusive and a diluent.

7. As new products of manufacture, the olefin oxids, derived from gas naphtha having a slight ethereal odor, insoluble in water,

ranging in specific gravity from about 0.830 to about 0.855, and in boiling points from about 70 C. to about 145 0. according to their carbon content, being colorless and readily miscible with the usual organic solvents, ether, alcohol, acetone, benzin, benzol, carbon tetrachlorid, and having as a distinguishing chemical property that of combining with hydrochloric acid, with formation of the corresponding chlorhydrins. Witness my hand this 19th day of January 1909, at New York, N. Y.

HENRY V. WALKER. Witnesses:

WILLIAM R. BAIRD, STEPHEN S. NEWTON. 

